Sulfonic-acid salt and process of making same.



UNITED STATES PATENT OFFICE.

LUDWVIG OTTO HELMERS, OF HAMBURG, GERMANY, ASSIGNOR TO IOHTHYOL GESELLSCHAFT OORDES, HERMANNI 82; (30., OF HAMBURG, GERMANY.

SULFONlC-ACID SALT AND PROCESS OF MAKING SAME.

SPECIFICATION formingpart of Letters Patent him 722,506, dated March 10, 190 3.

Application filed September 2, 1899- To all whom it may concern.-

Be it known that I, LUDWIG OTTO H ELMERS,

a subject of the Emperor of Germany, residing at Hamburg, in the German Empire, have invented certain new and useful Improvements in Sulfonic Acid Salts of Alkaline Earthy Metals and Metals Proper and Their Sulfonic Acids and Processes of MakingSame, of which the following is a specification.

In the specification of my United.States Patent No. 671,135 I have described a process of producing sulfonic acids that form permanent metal salts soluble in water. The primary material of these substancesis sulfurated hydrocarbons, and therefore the sulfonic acids resulting from the action of sulfuric acid orits substitutes on sulfureted hydrocarbons contain sulfur in the form of the sulfo group SO H (derived from the sulfuric acid used) and also in. the form of sulfid in combination with carbon and hydrogen, (derived from the sulfureted hydrocarbons.) Experiments nowhave shown that also the sulfonized products obtained by the action of sulfuric acid on hydrocarbons free from sulfur, such as bituminous-coal oil, paraffin-oil, resinoil, (see United States Patent No. 495,124,) yield sulfonic acids forming permanent metallic salts soluble in water, provided these sulfonized products are treated in the manner explained in the specification of my aforesaid United States Patent No. 671,135. These sulfonic acids contain sulfur only in the form of the sulfo group and are free from sulfur in the form of sulfid.

Hitherto it has been assumed that the sulfonic-acid salts of alkaline earths and heavy metals (with the only exception of the salts of antimony and mercury) are insoluble in water. (See United States Patent No. 495,124.) However, a closer examination has proved that also in this case analogous to the sulfonized products obtained from sulfureted hydrocarbons a part of the sulfonized products yield alkaline earth salts and metal salts which are soluble in water and that these salts and the corresponding acids possess strong reducing qualities. On account of this property the salts with an easily-reduci- 5o ble base are also not very permanent. Permanent salts, however, may be produced if distillation, and evaporated to dryness.

Seria N0; 729.355. (No specimens.

the acid resulting from the just-mentioned soluble alkaline-earth salts is oxidized and the oxidized acid afterward converted into the metallic salt by neutralizing with the corresponding metallic oxid, hydroxid, or carbonate.

The following example will more clearly elucidate the present invention:

1 The product obtained by the action of one kilogram of fuming sulfuric acid upon one kilogram of resin-oil is poured into water and the solution neutralized with milk of lime, the liquid decanted from the sediment, then filtered, the filtrate saturated with-carbonic acid and evaporated to a small volume. remaining liquid, to which about the double volume of alcohol is to be added in order to remove the still-dissolved calcium sulfate, is thereupon filtered, freed from the alcohol by The residuethe lime salt of the sulfonic acid of the resin-oilis a brown powder readily soluble in water.

From the lime salt or another salt of the sulfonic acid the free acid is obtained by one of the usual methods. The metallic salts of this acid are not permanent; but after the acid has been oxidized metallic salts are obtained which form permanent aqueous solutions. These solutions in contradistinction to those of the guaiacol sulfonic-acid salts give no color with ferric chlorid.

In order to obtain, for example, a permanent silver salt, it is not necessary to prepare and isolate the free sulfonic acid or one'of its alkaline earthy salts, but it is most expedient to proceed in the following way: The product obtained by the action of one kilogram of fuming sulfuric acid upon one kilogram of resin-oil is poured into water and the solution neutralized with milk of lime, the liquid decanted from the sediment and filtered, the filtrate saturated with carbonic acid and evaporated to a small volume. The remaining liquid, to which about the double volume of alcohol is to be added in order to remove the still-dissolved calcium sulfate, is thereupon filtered, freed from the alcohol by distillation, and evaporated to dryness. The lime salt is dissolved in a small volume of water, and then the calcium precipitated by adding about The v double the volume of alcohol and sulfuric acid in a quantity corresponding to the amount of the calcium. The solution filtered from the precipitated sulfate of calcium is freed from the alcohol by distillation and then heated for several hours with one-half kilogram of a solution of peroxid of hydrogen the oxidized solution neutralized with silver oxid or carbonate, and the clear solution evaporated to dryness, preferably in vacuo. The silver salt thus porduced forms a reddish-brown amorphous powder easily soluble in water.

Having thus fully described my invention, what I claim as'new therein, and desire to secure by Letters Patent, is

1. The process of producing sulfonic-acid salts of alkaline earth and metallic bases soluble in Water, which consists in neutralizing the sulfonic compound obtained by the action of sulfuric acid upon hydrocarbons free from sulfur, with a suitable base, filtering off the liquid from the precipitated insoluble salt and evaporating the filtrate to dryness, substantially as set forth.

2. The process of producing sulfonic-acid salts of an easily-reducible metallic base soluble and permanent in water, which consists in neutralizing the sulfonized compound obtained by the action of sulfuric acid upon hydrocarbons free from sulfur, with a suitable base, filtering oflf the liquid from the precipitated insoluble salt, evaporating the filtrate to dryness, dissolving the residue in water, setting free the sulfonic acid in the solution by precipitating the base, oxidizing the solution, neutralizing the oxidized sulfonic acid with a metallic easilyreducible base and evaporating the precipitate to dryness, substantially as set forth.

3. The process of producing sulfonic-acid salts of an alkaline earthy base soluble in water, which consists in neutralizing the sulfonized compound obtained by the action of sulfuric acid upon hydrocarbons free from sulfur, with lime, filtering off the liquid from the precipitated insoluble salts, and evaporating the filtrate to dryness, substantially as set forth.

4. The process of producing sulfonic-acid salts of an easily-reducible metallic base soluble and permanent in Water, which consists in neutralizing the sulfonized compound obtained by the action of sulfuric acid upon hydrocarbons free from sulfur, with lime, filtering off the liquid from the precipitated insoluble salt, evaporating the filtrate to dryness, dissolving the lime salt in water, setting free the sulfonic acid in the solution by precipitating the lime, oxidizing the solution, neutralizing the oxidized sulfonic acid with silver oxid, and evaporating the liquid to dryness, substantially as set forth.

5. As a new product of manufacture the herein-described sulfonic-acid salts consisting of an alkaline earthy base and a sulfonicacid compound derived from hydrocarbons free from sulfur, combined with sulfuric acid, which salts form a reddish-brown amorphous powder, are soluble in water, permanent in their solution and give no color'with ferric chlorid in aqueous solution, substantially as set forth.

6. As a new product of manufacture the herein-described sulfonicacid salts consisting of a metallic base and a sulfonic-acid compound, derived from hydrocarbons free from sulfur, combined with sulfuric acid, which salts form a reddish-brown amorphous powder, are soluble in water, permanent in their solution and give no color with ferric chlorid in aqueous solution, substantially as set forth.

LUDWIG OTTO HELMERS.

Witnesses:

ALEXANDER SPECHT, E. H. L. MUMMENHOFF. 

